Artificial mass and process for making the same



Patented July 31, 1934 UNITED STATES ARTIFICIAL MASS AND PROCESS FOR MAKING THE SAME Herbert Hiinel, Vienna, Austria, assignor to Beck, Kollcr & Company, Detroit, Michigan No Drawing. Originalapplication May 11 1929,

Serial No; 362,460. Divided and this application January 2, 1931, Serial No. 506,296. In Austria August 6, 1927 8 Claims. (Cl. 260-4) The invention relates to a process for producing organic masses of more or less high molecular weight, which may be employed alone or in combination with filling materials as the basis of 5 pressed articles, as binding agents or for preparing varnishes and other coating or impregnating agents and the like.

The present application is a division of my prior application Serial No. 362,460, filed May 11, 1929, now Patent 1,800,296, which latter application is a continuation in part of my still earlier application Serial No. 218,587, filed Sept. 9, 1927, now Patent 1,800,295, entitled Condensation product and process for preparing same.

The process according to this invention consists in heating condensation products of low molecular weight, obtained with the aid of alkaline contact agents from such phenolic substances, which only possess two particularly reactive positions in the molecule and which, when heated alone, change into an infusible condition, to elevated temperatures together with any ester-like chemical substances. The reaction is accompanied with the formation of water and is to be regarded as a condensation reaction.

As the particularly reactive positions in a phenol are to be regarded, as is known the two ortho and the para position to the phenol-hydroxyl. One of these positions must therefore be occupied by a substituent. Examples of the latter are, a hydrocarbon radical (alkyl, aryl, aralkyl, hydroaromatic radical) or an oxalkyl radical or chlorine. Other substituents have proved to be less suitable. One or both of the meta positions may on occasion also be occupied. The following are examples of a few easily obtainable phenolic bodies of this kind: 0- and p-cresol, certain xylenols, carvacrol, thymol, p-tertiary butyl phenol and amyl phenol, pbenzyl phenol, as well as the corresponding derivatives of m-cresol, guaiacol, oand p-chlorophenol, oand p-chloro-m-cresol, etc.

Derivatives of the dioxybenzenes, i. e. di-valent mono-nuclear phenolic substances, are also suitable, the conditions however, are somewhat more complicated and not quite clear. As, moreover, the use of these substances is lacking in economy, they will not be further discussed.

On the other hand, the applicability of all those di-valent, di-nuclear phenolic substances, which are derivatives of the pp-di-oxy-di-phenylmethane, is to be emphasized. They are easily obtainable and result from the condensation of 2 mols of phenols or certain homologues with 1 mol of a carbonyl compound with the aid of hydrochloric acid or, if possible, other acids. In

the present case the most suitable phenol homologue is o-cresol, from which di-o-cresylol methane, ethane, propane or butane, is obtained according to whether condensation has been efiected with formaldehyde and its homologues or acetone 00 and its homologues. Cyclic ketones may also be employed in which case, for example, di-ocresylol cyclohexane or di-o-cresylol methylcyclohexane corresponding to the above compounds, are obtained. Phenol, however, may also 5 be used as starting material and, for example, 2 atoms of chlorine be introduced as substituents,

in the di-phenylol compounds thus obtained. In all these cases di-nuclear di-valent phenolic substances are obtained, all of which also only possess 10 two reactive positions in the molecule.

It is to be observed that condensation products from phenolic substances with only one reactive position in the molecule may also be employed. Their yield is, however, considerably less and the action only a very limited one, which is in agreement with the fact that, when heated alone, they cannot be converted into the infusible state. Phenolsof this kind are, for example, certain xylenols, pseudo-cumenol, creosol, chlor-o-cresol so and chlor-p-cresol.

aand'B-naphthol behave in a surprising man-' ner like the last mentioned phenols, although they actually belong to the first mentioned group.

The condensation products obtained from 35 formaldehyde and phenols, in which all three particularly reactive positions are unoccupied, however, are unsuitable "for the process, because, on heating, they rapidly further condense in such a way that insoluble masses of resin in coarse or fine condition are separated or that they at least become permanently turbid.

The mechanism of the reaction doubtless is that the molecules of the condensation product do not only react with one another with the formation of products of high molecular weight, but also with the ester-likesubstance or with its components. The alcoholic hydroxyl groups-of the condensation product, known as very reactive, may bring about unions so that multivalent ester components may be in part formed. This possibility in conjunction with the first mentioned reaction may lead to the formation of individual gelatinous or rubber-like infusible and insoluble masses. It is a known fact that, in the esterification of nearly equivalent quantities of polybasic carboxylic acids with polyvalent alcohols, infusible masses result. Similarly the possible production in this case of gelatinous masses resembles the similar phenomenon in the continuous polymerino In general all possible ester-like substances.

have proved to be applicable to the reaction. Even low molecular completely crystalloid esters,

for example benzoic acid esters of mono-valent' alcohols, yield according to the proportions employed, thin to highly viscous oils or gelatinous masses. Esters of mono-valent alcohols with polyvalent components may yield, even with lesser quantities of the same condensation product, gelatinous end products. The full value of the process, however, is only reached when the ester-like substance is one which is not easily volatilized orbetter is practically non-volatile. Thus products, which have been obtained by esteriflcation on both sides of a suitable mixture of polyvalent and mono-valent components are very advantageous in this sense. On one of the two sides, only a polyvalent component can suitably be represented. When suitable proportions are employed such ester-like substances are soluble and far from a rubber-like infusible condition. Under certain circumstances even small quantities of a condensation product produce the above described effect.

The present process enables the proportions of ester components to be replaced to a very considerable extent by the usually cheap mono-basic acid. The final end product, however, shows technically very similar properties to those of an ester with a comparatively high proportion of the usually expensive polybasic acid. The economic advantage of the process is thus very evident, the more so as at the same time a-considerable saving in polyvalent alcohol is also effected.

It is, moreover, not necessary to start with the individual components of the esters as such, it is also possible to replace the mono-basic acids (for example higher fatty acids etc.) more or less by their glycerides (i. e. fat or fatty oil), in which case individual esters are nevertheless obtained apparently owing to re-esterification. In any case when they react with the condensation products in the later stages of the process, they behave as though they had been directly obtained. Purely physical mixtures of complicated esters of this kind and ordinary fatty acid glycerides etc. may of course also be subjected together to the reaction with the condensation products. In cases such as these the economic advantage is, of course, still greater.

The mono-basic as well as the poly-basic acids may be aliphatic, saturated or unsaturated, aro matic or hydroaromatic, they may or may not contain alcoholic or phenolic hydroxyl groups (1. e. they may or may not be oxy acids). Glycerine is the most important example of a polyvalent alcohol, alcohols of higher valency or the only di-valent glycol may, however also be employed.

Finally it should be again emphasized that esters of every kind may be employed for the reaction. The hydroxyl compound may also be a phenol and the acid an inorganic acid. A condition for the success of the reaction is merely that the condensation product, which at elevated temperature first gives off its mechanically combined water, is then soluble in the ester-like substance (at least when hot) before a condensation reaction takes place as otherwise, of course, no mutual reaction can result. This result is obtained .by suitably choosing the substituents in the phenolic substance. It may in some cases be convenient for instance if the ester-like compound is per se a resin-like substance of high melting point to carry out the process in the presence of a suitable solvent; the latter may, if re quired, be removed by distillation when the reaction is over.

The preparation of the condensation products is effected inknown manner, preferably by leaving the phenolic substance or a mixture of several phenols and aqueous formaldehyde together with at least so much alkali hydroxide, that a clear solution results, if necessary with the aid of alcohol, to react for a long time at room temperature or slightly elevated temperature. The resulting reaction product is then precipitated with acid-reacting agents. Formaldehyde in excess of the equimolecular quantity is with advantage employed.

The above described effect may be utilized in different ways. The quantity of condensation product employed may be such that, if the condensation reaction with the ester were carried to completion an insoluble, rubber-like produce would result, in which case the reaction must be interrupted before completion, if necessary even in its initial stage. In this case the solutions of the resulting products yield coatings, which become particularly hard at furnace temperatures. If necessary, siccatives may also be added to the reaction product. Products of this kind resulting from an interrupted reaction are also particularly suitable for use as plastic masses. They may be employed with or without filling materials for the preparation of various commodities.

An alternative procedure is to employ the condensation product in such a quantity that even on complete condensation with the ester-like product an oily, possibly resin-like or wax-like end product is obtained, which more or less approaches the rubber-like condition without actually attaining it. An increase of the colloidal condition is at least efiected. In the case of solid, particularly resin-like esters, an increase of their melting point is, as a rule, effected as well. The heating of the product can in this case be carried to about 200220 C. for any desired time without any noteworthy increase of the colloidal condition being observed. The still soluble products or their solutions may be employed alone as the basis for paints or, in general, as raw materials for the production of varnishes and other coating masses. If the acid components or one of the components is derived from drying or semi-drying oils or from fatty oils which only thicken by the absorption of oxygen, a siccative may also be added and in this way, tough and hard'drying varnishes may be obtained.

In individual cases very special effects may also be obtained by means of the process. Thus for example, wood oil, even when condensed with only a small quantity of a suitable condensation product, loses its known disadvantageous manner of drying. A particularly hard, smooth and rapidly drying varnish may in fact be obtained in this way.

Examples (1) 6 parts of melissic palmitate (beeswax) are melted and stirred up with the liquid condensation product obtained from one part of p-tertiaryamyl phenol and one part of 30% formaldehyde. The temperature is then gradually raised to 240 C. Thebrown end product shows characteristic properties which differ from those of the beeswax itself. It is harder, more easily polished, more plastic and in thin layers more transparent and when poured out in thin plates is elastically pliable. When poured onto a smooth surface it displays considerable adhesive powers. In general the colloidal properties of the product are considerably increased, and the product itself to a certain extent assumes resin-like properties.

(2) 4 parts of melted beef tallow are stirred up with the viscous condensation product resulting from 1 part of p-tertiary-butyl-m-cresol and 1 part of formaldehyde 40% by volume gradually heated up to 190 C. and maintained for 1-1 hours at this temperature. The end product has the character of a very viscous oil and only sets when cooled with ice to a lard-like mass.

(3) 100 grms. of castor oil and the crystalline condensation product obtained from 40 grms. of p-cresol and 60 grms. of 30% formaldehyde are heated with stirring up to 180 C. and maintained at this temperature until a cooled sample shows rubber-like elastic properties. The product is soluble in benzene and benzene-alcohol mixtures, as well as in various other solvents, but not in alcohol alone. When mixed with a siccative a varnish is obtained which on drying becomes considerably hard. The product may also be added as a softener to other siccative-free varnishes.

(4) The thick oily condensation product obtained with the aid of alkali from 1 part of ptertiary-butyl phenol and 1 part of 30% formaldehyde by heating for 24 hours to 50-55 C. and precipitated with acids is introduced at about 130 C. into 10 parts of wood oil with stirring. The temperature is then gradually raised to 220 C. The end product has the viscosity of a castor oil and yields with a suitable quantity of siccative and on suitable dilution a varnish of excellent properties which dries clear extremely rapidly.

(5) A viscous condensation product obtained with the aid of alkali from 30 grms. of thymol and 40 grms. of 30% formaldehyde is introduced into and dissolved in 500 grms. of a moderately boiled mixture of wood oil and linseed oil. This mixture, so called honey-oil is prepared in the usual manner by heating a mixture of 1 part of wood oil and 3 parts of linseed oil for 4 hours at 280 C. It is-to be regarded as the mixed glycerine ester of mono-basic oleflne carboxylic acids and poly-basic olefine carboxylic acids obtained by partial polymerization. The temperature is gradually raised whilst stirring. After expelling the mechanically combined water the ,reaction mixture is clear even when cold. It is finally heated up to 220 C. The product is still soluble and when cold represents a sticky and very ropy mass. On adding a siccative a fairly hard and tough drying varnish is obtained.

(5a) The quantity of honey-oil in the foregoing example is diminished to 300 grms. and the reaction mixture only heated to 160 C.

The highly viscous oil, when suitably diluted, yields a coating agent (binding agent, impregnating agent etc.), which even without the addition of a siccative or without absorbing oxygen from the air yields on heating to 160-200 C. a tenaciously adhesive coat etc. For this process vbasis for fumace-drying varnishes.

1 hour to 10 minutes are required according to the temperature employed. With the addition of siccatives a coat of pre-eminent hardness and resisting power is obtained at this temperature.

(6) A condensation product of low molecular weight obtained from 70 grms. of o-cresol and 100 grms. of 30% formaldehyde is dissolved with heating in 200 grms. of tricresyl phosphate and the mixture heated to 160 C. until a sample on cooling shows a highly viscous'ropy .oil. It is soluble in benzene hydrocarbons and other solvents. It may be employed, for example, as the On continued heating to 160 C. or higher a rubberlike to wood oil gelatinuous mass is obtained.

(7) 100 grms. of succinic acid, 150 grms. of lactic acid (100%) and 10 grms. of glycerine (98%) are heated to 160-200 C. until a soft resin-like product with an acid number of about 25 is obtained. At about 100-120 C. the crystalline condensation product obtained from 30 grms. of p-chlorophenol and 35 grms. of 30% formaldehyde is introduced and soon goes into solution. The temperature is gradually raised to 220 C. A soft resin having rubber-like elastic properties which is completely soluble in acetone and alcohol-benzene mixtures is obtained.

(8) A condensation product resulting from 55 grms. of p-chlor-m-cresol and 55 grms. of formaldehyde (40% by volume) is added with heating to the fairly hard and brittle resin-like esteriflcation product prepared as in Example 7 from 100 grms. of succinic acid, 160 grms. of salicylic acid and 100 grms. of glycerine and the mixture caused to react by raising the temperature to about 200 C. Without an apparent increase in the melting point of the resin-like product being observed a resin of marked shellac-like properties is obtained. The resin-like condition in this case is without doublt very considerably increased. The product is soluble in acetone and other solvents and may be employed for preparing polishes and the like. Its solutions may further be mixed both with nitro-cellulose and with acetylcellulose varnishes. In both cases clear satisfactorily adhering films are obtained.

(9) The ester-like semi-liquid reaction product obtained from 150 grms. of citric acid (crystalline), 100 grms. of ricinoleic acid, 100 grms. of salicylic acid and 115 grms. of glycerine on the one hand and 45 grms. of p-cresol di-alcohol on the other hand are caused to react together at about 180 C. A soft, very tenaciously elastic pale resin is obtained, which is soluble in alcohol up to the proportion of 1:1, but soluble in benzene-alcohol mixtures, in acetone, as well as in ester-like solvents in any proportion. It is especially suitable as addition to nitrocellulose varnishes.

(10) The condensation product obtained as in Example 6 is condensed with the thick oily ester obtained from 100 grms. of phthalic anhydride, 100 grms. of oleic acid and 65 grms. of ethylene glycol. A soft, rubber-like, elastic resin is obtained, which is soluble in benzene hydrocarbons as well as other solvents and is very suitable as an addition to nitrocellulose varnishes.

(11) The condensation product resulting from 3 parts of xylenol (1:4: 5) and 4 parts of 30% formaldehyde is added to an ester having an acid number of 30 and obtained from 6 parts of d-tartaric acid, 4 parts of benzoic acid and.4 parts of ethylene glycol. A soft soluble resin, which is elastic like rubber, is obtained as in Example 10.

(12) 4 parts of phthalic anhydride, 6 parts stearic acid and 3 parts of glycerine are esterifled together at 180-220 C. until an acid number of about 20 is reached. The product rapidly sets at room temperature to a. cloudy wax-like mass, which is somewhat sticky to the touch. The waxlike character is also manifested in its solutions, which, when poured out in thin layers, allow the solvent to evaporate very slowly.

100 grms. of o-cresol and 20 grms. of methyl ethyl-ketone are condensed with the aid of concentrated hydrochloric acid (37%). The reaction product is a mixture of o-cresoland di-ocresylol-butane. It is condensed at room temperature with 100 grms. of formaldehyde (40% by volume) with the aid of caustic soda and the condensation product precipitated with acid after about two weeks.

300 grms. of the ester-like product and half of the condensation product obtained above are heated together to 230 C. The resulting product represents at about 35 C. a soft, elastic resin-like transparent mass. Even on cooling to room temperature it is first clear and elastically flexible. After a few hours it merely becomes translucent and is then fairly brittle and easily friable. It is soluble in benzene hydrocarbons. Its solutions, when poured out in thin layers, allow the solvent easily to evaporate. The layer of product which remains is first clear, but after some time becomes cloudy like wax and possesses to a high degree the power of repelling water.

(13) 220 grms. of the ester-like product obtained as in Example 12 are heated to 150 C. with the remaining half of the condensation product obtained in the same example, until a cooled sample shows properties similar to those of the end product obtained in Example 12. The product like the latter is soluble in-benzene and the like. The solutions yield a temporarily clear film, which may be hardened at 150-200 C. and which adheres well to the coated surface, possesses strong water-repelling powers and remains permanently clear. The product itself, mixed with filling agents of any kind, may be employed for preparing compressed substances.

(14) The ester of acid number 10 obtained from 50grms. of sebacic acid, 100 grms. of technical abietic acid and 30 grms. of glycerine and which represents a soft sticky resinous mass, is worked up in the usual manner with the crystalline oily condensation product obtained from 13 grms. of guaiacol and 18 grms. of 30% formaldehyde. A resin somewhat softer than shellac is obtained, which, at the temperature of its melting point, is elastic like rubber. It is soluble in benzene hydrocarbons, acetone, etc., and miscible to a clear solution with nitrocellulose in any proportion.

(15) 2 parts of o-cresol and 1 part of technical methyl-cyclohexanone are condensed with the aid of hydrochloric acid. The reaction product consists of three isomers of di-o-cresylol-methylcyclohexane CH3-C6H9=(CH3-C6H3OH)2 and represents a thick oily mass permeated with separated crystals. It is condensed by means of caustic alkali at room temperature with 2 parts of formaldehyde (40% by volume) and the thick oily condensation product then separated with acids.

The latter is worked up with 15 parts of an ester obtained from 100 grms. of camphoric acid, 250 grms. of abietic acid and 65 grms. of glycerine and which represents a fairly brittle resin with an acid number of 20 and a melting point of 85 C. On condensing the latter with the condensation product, a very hard resin melting about 30 C. higher is obtained. By relatively increasing the condensation product a resin can be readily obtained, which is extremely hard and at the temperature of its melting point represents a rubber-like elastic mass. It is soluble in benzene hydrocarbons and yields clear films when mixed with nitrocellulose.

(16) (a) 76 grms. of benzyl chloride are slowly added with gentle heating at the start to 108 grms. of technical m-cresol containing 60% of pure m-cresol. In the simultaneous presence of a catalyst consisting of about 5 grms. of dry zinc chloride the reaction starts fairly quietly and may, if necessary, be later assisted and brought to completion by again heating. The benzyl group merely enters the m-cresol as a substituent with the removal of HCl, most probably in the para position, possibly also in the ortho position. According to the work of Beilstein, the position of the benzyl group is not known. The p-cresol apparently remains untouched. The oily reaction product is repeatedly washed with hydrochloric acid-containing water and then 180 grmsJof 30% formaldehyde added together with so much caustic alkali that after shaking clear solution results. After about 2 weeks the condensation product is precipitated.

(b) 250 grms. of' alcohol-soluble Manila are melted at 230-240 C. with 1000 grms. of colophony and, if necessary, the melt freed from dirt particles by filtration through a fine sieve. The mixture is then esterifled at a temperature of 240-280 C. with 150 grms. of glycerine (sp. g.

Manila copal contains polybasic resin acids.

The condensation product is gradually introduced at 170 C. into this mixed ester and the temperature then raised to 250 C. The end product is hard and tough and readily soluba in drying oils.

(17) The thick oily esterification product obtained from 4 parts of phthalic anhydride, 6 parts linoleic acid, 2 parts of c'olophony and 3 parts of glycerine are heated to 150 C. with the condensat ion product obtained from 2 parts of butyl phenol and 2 parts of 30% formaldehyde until a sample when cold represents a soft rubber-like elastic mass. The product is not only soluble in benzene hydrocarbons. but also in oil of turpentine and mineral spirits and yields, with or without the addition of siccatives, a varnish which dries very hardat furnace-temperature.

4-5 parts of the linoleic acid employed for the above ester may be replaced by linseed oil. It only takes considerably longer until a uniformly clear reaction mass is formed.

(18) The thick oily esteriflcation product having an acid number of 30 obtained from 50 grms. of phthalic anhydride, 150 grms. of ricinoleic acid and 50 grms. of manmte, is condensed at 180 C. with the crystalline condensation product obtained from 30 grms. of a mixture of oand pchlor-m-cresol and 30 grms. of formaldehyde (40% by volume). The mixture of phenolic substances is obtained by chlorinating the m-cresol dissolved in glacial acetic acid with the calculated quantity of elementary chlorine with ice cooling, and consists mainly of the para compound.

The end product is very soft and elastic like rubber, it may be diluted to a limited extent with alcohol, in any proportion with benzene hydrocarbons and ester-like solvents and may be employed as an addition for nitrocellulose varnishes. With the addition of siccatives it yields a hard drying varnish.

(19) The soft stick esteriflcation product obtained from 100 grms. of phthalic anhydride, 100 grins. of methyl cyclo-hexanol and 30 grms. of glycerine is heated to 140-200 C. together with a condensation product resulting from grms. of di-chlor-di-phenylol-propane and grins. 30% formaldehyde. A resin-like product, somewhat softer than shellac, results, which like the latter, has rubber-like elastic properties at the temperature of its melting point. It can with advantage be employed as a resin for nitrocellulose varnishes.

(20) ;grms. of crystallized citric acid, 200 grms. of benzyl alcohol are heated together in a distillation flask until a temperature of 250 C. is reached. The benzyl alcohol distilled over with the water of crystallization and reaction is separated therefrom, re-introduced into the flask, the above described operation being then repeated. Finally the unchanged benzyl alcohol is removed by applying a vacuum. The reaction product. which remains in the flask amounts to about 135 grms. and has an acid number of 90-100 about 25 grms. of water are collected in the receiver. That means that one carboxylic group has been esterified and partial formation of anhydride has taken place. 50 grms. of oleic acid and 42 grms. of glycerine are now added and the whole is heated to 250 C. until an acid number of 10 is reached. The light brown product is a thick liquid having the consistency of a thick boiled linseed oil.

The condensation product obtained as described in Example 18 is incorporated at a temperature below 140 0., the temperature being then gradually raised up to 220 C. The final product is a resin, which is soft at ordinary temperature, of rubber-like elasticity, soluble in benzene hydrocarbons, ester-like solvents and so on, and may be added to nitrocellulose varnishes in any desired proportion.

In the following claims the expression soluble artificial masses is intended to designate bases for coatings of all kinds, particularly varnishes, and bases for impregnating agents, binders and for all sorts of commodities.

The acids and their anhydrides are to be considered as equivalent in forming the esters.

What I claim is:

1. A soluble artificial mass produced by reacting (1) a condensation product obtained by esterifying a polyhydric alcohol with a carboxylic acid including a substantial quantity of sebacic acid, with (2) a condensation product of an aldehyde and a phenol having at the utmost two unsubstituted particularly reactive positions.

2. A process of producing artificial masses which comprises combining (1) a condensation product obtained by esterifying a polyhydric alcohol with a carboxylic acid including a substantial quantity of sebacic acid, with (2) a condensation product of an aldehyde and a phenol having atv the utmost two unsubstituted particularly reactive positions.

3. A soluble artificial mass produced by reacting (1) an esterified polyhydric alcohol with (2) the product obtained by condensing together guaiacol and formaldehyde, the polyhydric alcohol being esterified with an organic acid.

4. A method of producing resinous bodies of high molecular weight which comprises reacting (1) an esterified polyhydric alcohol with (2) the product obtained by condensing together guaiacol and formaldehyde, the polyhydric alcohol being esterified with an organic acid.

5. Asoluble artificial mass comprising (1) a condensation product of an aldehyde with a phenol having not more than two unsubstituted particularly reactive positions in the molecule reacted with (2) a condensation product of a polyhydric alcohol, abietic acid and sebacic acid.

6. A soluble artificial mass comprising (1) a condensation product of an aldehyde with a phenol having not more than two unsubstituted particularly reactive positions in the molecule reacted with (2) a condensation product of glycerol, abietic acid and sebacic acid.

7. A soluble artificial mass produced by reacting the ester-like product obtained from sebacic acid, abietic acid and glycerine, with the product obtained by condensing together guaiacol and formaldehyde.

8. A process for producing soluble artificial masses which comprises reacting the ester-like product obtained from sebacic acid, abietic acid and glycerine, with the product obtained by condensing together guaiacol and formaldehyde.

HERBERT 36m. 

